京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第19379号 / 農博第2149号 / 新制||農||1037(附属図書館) / 学位論文||H28||N4959(農学部図書室) / 32393 / 新制||農||1037 / 京都大学大学院農学研究科森林科学専攻 / (主査)教授 髙部 圭司, 教授 髙野 俊幸, 教授 杉山 淳司 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DGAM

No description available.

Two-dimensional (2D) materials have properties that are often different from their three-dimensional (3D) bulk form. Many of these materials are stable at ambient conditions, which allows them to be integrated with other 2D- or 3D-materials to form heterostructures. Integration of various dimensional materials attains unique electrical and optical properties that aid in developing novel electronic devices. The interface of the heterogeneous integration of these films can exhibit a weak van der Waals-like bonding. In this thesis, an advanced characterization (from atomic to millimeter resolution) of various dimensional materials with weakly bonded interfaces is developed and employed to understand their behavior at scale. First, a large-area single-crystal cadmium telluride thin film is grown incommensurately and strain-free to a sapphire substrate despite a significant 3.7% lattice mismatch. The film remarkably delaminates as a bulk single crystal film due to an atomically thin tellurium that spontaneously forms at the interface. Aberration-corrected electron microscopy and spectroscopy reveal both the van der Waals-like structure and bonding at the film/substrate interface. Second, a large-area atomically thin gallium is intercalated at the interface of epitaxial graphene. Correlative microscopy workflows are applied to understand the thickness uniformity and area coverage of the 2D–gallium over few millimeters of the sample. Utilizing multiple correlative methods, SEM image contrast is found to be directly related to the presence of the intercalated gallium. The origin of the SEM contrast is investigated as a function of the surface potential. Then, the heterostructure characterization is scaled up over a few square millimeter areas by segmenting SEM images, each acquired with nanometer-scale resolution. Additionally, transmission electron microscopy is applied to investigate the interface of gallium–SiC, the gallium air–stability, and the role of the substrate on the heteroepitaxial growth of 2D–gallium, which charts a path for further development of these materials. / Thesis / Doctor of Philosophy (PhD)

InGaAs quantum dot chains were grown with a low-temperature variation of the Stranski-Krastanov method, the conventional epitaxial method. This new method seeks to reduce indium segregation and intermixing in addition to giving greater control in the growth process. We used photoluminescence spectroscopy techniques to characterize the quality and electronic structure of these samples. We have recently used a transmission electron microscope to show how the quantum dots vary with annealing temperature. Some questions relating to the morphology of the samples cannot be answered by photoluminescence spectroscopy alone. Using transmission electron microscopy, we verified flattening of the quantum dots with annealing temperature and resolved the chemical composition with cross-section cuts and plan view cuts.

In NiTi, a reversible thermoelastic martensitic transformation can be induced by temperature or stress between a cubic (B2) austenite phase and a monoclinic (B19') martensite phase. Ni-rich binary compositions are cubic at room temperature (requiring stress or cooling to transform to the monoclinic phase), while Ti-rich binary compositions are monoclinic at room temperature (requiring heating to transform to the cubic phase). The stress induced transformation results in the superelastic effect, while the thermally induced transformation is associated with strain recovery that results in the shape memory effect. Ternary elemental additions such as Fe can additionally introduce an intermediate rhombohedral (R) phase between the cubic and monoclinic phase transformation. This work was initiated with the broad objective of connecting the macroscopic behavior in shape memory alloys with microstructural observations from transmission electron microscopy (TEM). Specifically, the goals were to examine (i) the effect of mechanical cycling and plastic deformation in superelastic NiTi; (ii) the effect of thermal cycling during loading in shape memory NiTi; (iii) the distribution of twins in martensitic NiTi-TiC composites; and (iv) the R-phase in NiTiFe. Both in situ and ex situ lift out focused ion beam (FIB) and electropolishing techniques were employed to fabricate shape memory alloy samples for TEM characterization. The Ni rich NiTi samples were fully austenitic in the undeformed state. The introduction of plastic deformation (8% and 14% in the samples investigated) resulted in the stabilization of martensite in the unloaded state. An interlaying morphology of the austenite and martensite was observed and the martensite needles tended to orient themselves in preferred orientations. The aforementioned observations were more noticeable in mechanically cycled samples. The observed dislocations in mechanically cycled samples appear to be shielded from the external applied stress via mismatch accommodation since they are not associated with unrecoverable strain after a load-unload cycle. On application of stress, the austenite transforms to martensite and is expected to accommodate the stress and strain mismatch through preferential transformation, variant selection, reorientation and coalescence. The stabilized martensite (i.e., martensite that exists in the unloaded state) is expected to accommodate the mismatch through variant reorientation and coalescence. On thermally cycling a martensitic NiTi sample under load through the phase transformation, significant variant coalescence, variant reorientation and preferred variant selection was observed. This was attributed to the internal stresses generated as a result of the thermal cycling. A martensitic NiTi-TiC composite was also characterized and the interface between the matrix and the inclusion was free of twins while significant twins were observed at a distance away from the matrix-inclusion interface. Incorporating a cold stage, diffraction patterns from NiTiFe samples were obtained at temperatures as low as -160ºC. Overall, this work provided insight in to deformation phenomena in shape memory materials that have implications for engineering applications (e.g., cyclic performance of actuators, engineering life of superelastic components, stiffer shape memory composites and low-hysteresis R-phase based actuators). This work was supported in part by an NSF CAREER award (DMR 0239512).

Thin-film solar cells are potentially low-cost devices to convert sunlight into electricity. Improvements in the conversion efficiencies of these cells reduce material utilization cost and make it commercially viable. Solar cells from the Thin-Film Physics Group, ETH Zurich, Switzerland and the Florida Solar Energy Center (FSEC), UCF were characterized for defects and other microstructural features within the thin-film structure and at the interfaces using transmission electron microscopy (TEM). The present thesis aims to provide a feedback to these groups on their deposition processes to understand the correlations between processing, resulting microstructures, and the conversion efficiencies of these devices. Also, an optical equipment measuring photocurrents from a solar cell was developed for the identification of defect-prone regions of a thin-film solar cell. The focused ion beam (FIB) technique was used to prepare TEM samples. Bright-field TEM along with scanning transmission electron microscopy (STEM) and energy dispersive X-ray spectroscopy (EDS) including elemental distribution line scans and maps were extensively used for characterizing the absorber layer and interfaces both above and below the absorber layer. Energy-filtered transmission electron microscopy (EFTEM) was applied in cases where EDS results were inconclusive due to the overlap of X-ray energies of certain elements, especially molybdenum and sulfur. Samples from ETH Zurich were characterized for changes in the CIGS (Cu(In,Ga)Se2) microstructure due to sodium incorporation from soda-lime glass or from a post-deposition treatment with NaF as a function of CIGS deposition temperature. The CIGS-CdS interface becomes smoother and the small columnar CIGS grains close to the Mo back contact disappear with increasing CIGS deposition temperature. At 773 K the two sodium incorporation routes result in large differences in the microstructures with a significantly larger grain size for the samples after post-deposition Na incorporation. Porosity was observed in the absorber layer close to the back contact in the samples from FSEC. The reason for porosity could be materials evaporation in the gallium beam of the FIB or a processing effect. The porosity certainly indicates heterogeneities of the composition of the absorber layer near the back contact. A Mo-Se rich layer (possibly MoSe2) was formed at the interface between CIGS/CIGSS and Mo improving the quality of the junction. Other chemical heterogeneities include un-sulfurized Cu-Ga deposits, residual Se from the selenization/ sulfurization chamber in CIGS2 and the formation of Cu-rich regions which are attributed to decomposition effects in the Ga beam of the FIB. Wavy absorber surfaces were observed for some of the cells with occasional discontinuities in the metal grids. The 50 nm thick CdS layer, however, remained continuous in all the samples under investigation. For a sample with a transparent back contact, a 10 nm Mo layer was deposited on ITO (indium tin oxide) before deposition of the CIGS2 (Cu(In,Ga)S2) layer. EFTEM maps indicate that a MoS2 layer does not form for such a Mo/MoS2-ITO back contact. Instead, absorber layer material diffuses through the thin Mo layer onto the ITO forming two layers of CIGS2 on either side of Mo with different compositions. Furthermore, an optical beam induced current (OBIC) system with micron level resolution was successfully developed and preliminary photocurrent maps were acquired to microscopically identify regions within a thin-film solar cell with undesirable microstructural features. Such a system, when fully operational, will provide the means for the identification of special regions from where samples for TEM analysis can be obtained using the FIB technique to study specifically the defects responsible for local variations in solar cell properties.

The filiform-like corrosion of Magnesium (Mg) alloys AZ31B and AM30 was investigated with electrochemical and microanalytical techniques. Potentiodynamic polarization testing and scanning vibrating electrode technique (SVET) measurements confirmed the “differential electrocatalytic” mechanism previously reported for filiform and filiform-like corrosion on pure Mg and AZ31B. Transmission electron microscopy (TEM) and Auger electron spectroscopy (AES) revealed that the MgO corrosion filaments on both alloys were likely a product of the direct reaction of Mg and water (H2O), responsible for the rapid hydrogen (H2) evolution observed at the propagating corrosion fronts. TEM analysis also revealed through-thickness cracks and noble intermetallic particles within the corrosion filaments and noble metal enrichment at the corrosion filament/metal interfaces, which were proposed to play significant roles in the cathodic activation of the corrosion filaments. The higher susceptibility of the AZ31B alloy to cathodic activation versus AM30 suggested that Zinc (Zn) has a detrimental effect on the resistance of Magnesium-Aluminum-Zinc (Mg-Al-Zn) alloys to filiform and filiform-like corrosion. / Thesis / Master of Applied Science (MASc)

Advances in micro/nano-fabrication, thin electron transparent materials, holder designs, and acquisition methods have made it possible to perform meaningful experiments using liquid electron microscopy (liquid EM). Liquid EM provides researchers with micro-to-nano scale tools to explore biomaterials in liquid environments capable of capturing dynamic in situ reactions, providing characterization means in mimetic conditions to the human body. However, these emerging techniques remain in their infancy; limited work presents best practice strategies, and several challenges remain for their effective implementation, particularly for beam-sensitive, soft biological materials. This thesis seeks to address these shortcomings by exploring strategies for liquid EM of biomaterials and real-time dynamic processes using two key methods: room temperature ionic liquid (RTIL) treatment for scanning EM (SEM) and liquid cell transmission EM (TEM). With these techniques, the research explores the characterization of hard-tissue systems relevant to bone and seeks to provide new methods of exploring structurally biological culprits behind diseases like COVID-19. Research in this thesis is presented by increasing complexity, touching on three themes: (i) exploring liquid EM for the first time using RTILs for SEM of biological samples notably bone (static, micro-scale), (ii) developing new methods for high-resolution liquid biological TEM of viruses (static, nano-scale), and (iii) applying novel liquid TEM to dynamic biomineralization systems (dynamic, nano-scale). After review articles serve as introductory material in Chapter 2, in Chapter 3, healthy and pathological bone was explored in hydrated conditions with liquid SEM using a new workflow involving RTIL treatment, demonstrated to be highly efficient for biological SEM. Moving to the nanoscale, Chapter 4 presents a commercial liquid TEM option and a new liquid TEM clipped enclosure developed for imaging biological specimens, specifically virus assemblies such as Rotavirus and SARS-CoV-2. Combined with automated acquisition tools and low-dose direct electron detection, enclosures resolved high-resolution structural features in the range of ~3.5 Å – 10 Å and were correlatively used for cryo TEM. Chapter 5 applies these liquid TEM methods to study collagen mineralization, revealing in high-resolution the presence of precursor calcium phosphate mineral phases, important transitional phases to mineral platelets found in mineralized tissues. But – dynamic reactions were not captured, attributed to confinement effects, lack of heating functionality, and cumulative beam damage experienced. Chapter 6 overcomes these challenges by optimizing collagen-liquid encapsulation within a commercial liquid TEM holder mimicking physiological conditions at 37°C. Dynamic nanoscale interactions were highlighted, where evidence of the coexistence of amorphous precursor phases involving polymer-induced liquid as well as particle attachment was presented within this model. Several liquid TEM challenges remain particularly beam sensitivity and distribution for biomaterials, providing many exciting avenues in future to explore. Taken together, this thesis is advancing characterization through the development and applied use of new liquid EM strategies for studying biomaterials and dynamic reactions. Insights on these reactions and structures anticipate leading to a better understanding of diseases and treatment pathways, the key to moving Canada’s health care system forward. / Thesis / Doctor of Philosophy (PhD) / In the electron microscopy (EM) community, there is a need for improved methodologies for high-resolution liquid imaging of biological materials and dynamic processes. Imaging biological structures and reactions in hydrated biomimetic environments improves our understanding of their true nature, thus providing better insight into how they behave in the human body. While liquid EM methods have surged in publications recently, the field is still in its infancy; limited works present best practice strategies, and several challenges remain for their effective implementation. To address these shortcomings, this thesis aims to strategically explore the improvement of liquid EM of biomaterials and real-time dynamic processes through two key methods: room temperature ionic liquid treatment for scanning EM and liquid cell transmission EM. Using these novel techniques, the research explores the characterization of hard-tissue systems relevant to bone and seeks to provide new means of exploring structurally biological culprits behind diseases like COVID-19.

In dieser Arbeit wurde in situ TEM genutzt, um Phasendiffusionsprozesse in Echtzeit mit hoher räumlicher Auflösung während struktureller Übergangsphänomene in verschiedenen Systemen zu untersuchen, die durch eine zunehmende Anzahl von Einflussparametern wie Kristallorientierung oder Dehnung charakterisiert sind. Zur Entwicklung und Erprobung der Methode wurde die Interdiffusion an planaren Grenzflächen zwischen (Al,Ga)As-Schichten unterschiedlicher Zusammensetzung während des Glühens untersucht. Ein neuer hybrider Probenpräparationsansatz wurde verwendet, um die Interdiffusion in der Heterostruktur bei Temperaturen bis zu 800 Grad Celsius mit der in situ Weitwinkel-Dunkelfeld-Rastertransmissionselektronenmikroskopie (HAADF STEM) zu untersuchen. Die beobachtete Grenzflächenverbreiterung zeigte eine starke Abhängigkeit der Diffusionskoeffizienten von der lokalen Zusammensetzung von Al und Ga. Als nächstes wurde HAADF STEM verwendet, um die Phasenseparationsbildung von Bi-reichen Clustern in einem Ga(Sb,Bi)-Film direkt zu beobachten. Die Ergebnisse zeigten, dass sie sich durch spinodale Zersetzung bilden. Der komplexeste strukturelle Übergang, der in dieser Arbeit untersucht wurde, ist die Festphasenepitaxie (SPE) von Ge auf Fe3Si, die zur Bildung einer neuartigen epitaktisch stabilisierten FeGe2-Phase führt. Mittels in situ hochauflösendem (HR)TEM konnten die verschiedenen Schritte dieses Phasenübergangs alle in Echtzeit beobachtet werden. Die Ergebnisse zeigten, dass eine intermediäre CsCl-ähnliche Phase von FeGe2 zunächst durch einen diffusionsbegrenzten Prozess Schicht für Schicht von der Ge/Fe3Si-Grenzfläche aus wächst. Nach einer bestimmten Filmdicke wandelt eine zweite Umwandlung den Film in eine tetragonale Schichtstruktur von FeGe2 um. Dieser Prozess beginnt ebenfalls an der Grenzfläche zum FeGe2 und kann auf Gitterdehnung zurückgeführt werden. / In this work, in situ TEM was utilized to investigate phase diffusional processes in real time with high spatial resolution during structural transition phenomena in various systems which are characterized by an increasing number of impact parameters such as crystal orientation or strain. In order to develop and evaluate the experimental method interdiffusion at planar interfaces between (Al,Ga)As layers of different composition during annealing was investigated. A new hybrid sample preparation approach was used to investigate the interdiffusion in the heterostructure at temperatures up to 800 _C with in situ high angle annular dark field scanning transmission electron microscopy (HAADF STEM). The observed interface broadening revealed a strong dependence of the diffusion coefficients on the local composition of Al and Ga. Next in situ HAADF STEM was used to directly observe the phase separation formation of Bi-rich clusters in a Ga(Sb,Bi) film. The results showed that they form by spinodal decomposition. The most complex structural transition investigated in this work is the solid phase epitaxy (SPE) of Ge on Fe3Si resulting in the formation of a novel epitaxially stabilized FeGe2 phase. By using in situ high resolution (HR)TEM the different steps of this phase transition could all be observed in real time. The results showed that an intermediate CsCl-like phase of FeGe2 grows first by a diffusion limited process layer-by-layer from the Ge/Fe3Si interface. After a certain film thickness, a second transformation transforms the film into a tetragonal layered structure of FeGe2. This process also initiates at the interface to the FeGe2 and can be attributed to strain.

The objective of the current study was to determine the efficacy of 3% acetic acid in reducing Salmonella in pork trimming and the effects of such treatment on meat quality. For 15-s dipping and 5-log CFU/pork cube inoculation, only 0.2- to 0.3-log reduction was observed (P ≤ 0.026). Acetic acid worked best at 75 s and 50°C, providing 1.4-log reduction (P < 0.001), damaging Salmonella cell membranes. When an inoculated pork cube was placed at the geometrical center of 2.3-kg pork trimming, dipping at 50°C for 75 s only reduced Salmonella by 0.2 log (P = 0.040). Although dipping slightly increased lightness (P < 0.001) and decreased redness (P ≤ 0.008) on the meat surface, no inside color change was detected (P = 0.120). Neither lipid oxidation (TBARS, P = 0.644), protein solubility (P = 0.187), nor water-holding capacity (P = 0.076) were affected by treatments.